CN113800515B - Preparation method of nitrogen-doped activated carbon and multi-hydroxide/biomass porous carbon nano composite electrode material - Google Patents
Preparation method of nitrogen-doped activated carbon and multi-hydroxide/biomass porous carbon nano composite electrode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- 239000002028 Biomass Substances 0.000 title claims abstract description 29
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 241000080590 Niso Species 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
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- 238000001914 filtration Methods 0.000 claims description 5
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- 238000005406 washing Methods 0.000 claims description 5
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- 230000008014 freezing Effects 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 22
- 239000003610 charcoal Substances 0.000 abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- 229910020630 Co Ni Inorganic materials 0.000 description 43
- 229910002440 Co–Ni Inorganic materials 0.000 description 43
- 239000003990 capacitor Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
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- 238000004108 freeze drying Methods 0.000 description 4
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- 239000000758 substrate Substances 0.000 description 4
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910017709 Ni Co Inorganic materials 0.000 description 2
- 229910003267 Ni-Co Inorganic materials 0.000 description 2
- 229910003262 Ni‐Co Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000006479 redox reaction Methods 0.000 description 2
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
A preparation method of nitrogen-doped active carbon and multi-hydroxide/biomass porous carbon nano composite electrode material relates to a preparation method of active carbon and porous carbon nano composite electrode material. The porous biomass charcoal material is used for solving the technical problem that the specific surface area of the existing porous biomass charcoal material is small. The nitrogen-doped active carbon is prepared from corncob and NH 4 HCO 3 Carbonizing at high temperature to obtain; the preparation method of the multi-hydroxide/biomass porous carbon nano composite electrode material comprises the following steps: mixing NiSO 4 .6H 2 O、Co(NO 3 ) 2 .6H 2 O、AlCl 3 .6H 2 Dissolving O and nitrogen-doped active carbon in water to prepare a precursor solution; and transferring the precursor solution and ammonia water to a high-pressure kettle for hydrothermal synthesis to obtain the electrode material. The specific surface area of the nitrogen-doped active carbon reaches 800m 2 g ‑1 ~900m 2 g ‑1 . The specific capacitance of the multi-hydroxide/biomass porous carbon nano composite electrode material reaches 240-1836.7F . g ‑1 And can be used in the field of electrode materials.
Description
Technical Field
The invention relates to an active carbon and porous carbon nano composite electrode material and a preparation method thereof.
Background
As the large consumption of fossil fuels and environmental pollution increase, the demand for raw energy storage devices has increased, thus accelerating the research of high-performance devices and related electrode materials. Supercapacitors have attracted extensive attention and scientific research due to their excellent power density, long cycle life and fast charge-discharge kinetics. However, their widespread use is hindered by low energy density, and electrodes of highly conductive carbon materials such as graphene, carbon nanotubes, and the like are expensive. Therefore, the development of low-cost and high-capacitance nano-material electrodes has become the key to obtain high-performance super capacitors.
Among various nanomaterials, transition metal hydroxides have a series of advantages of outstanding redox activity, higher theoretical specific capacitance and the like. Compared with single-metal-based and double-metal-based nano hydroxides, the trimetallic-based compound has more active reaction sites and more redox states, and can show excellent electrochemistry and redox reaction kinetics. However, the application of metal oxide/hydroxide is severely limited by the characteristics of poor conductivity, easy agglomeration and the like, so that the introduction of a high-conductivity and high-stability substrate material is indispensable. The biomass charcoal material has the advantages of low cost, simple synthesis method, large specific surface area, adjustable porous structure and the like, and is a preferred substrate material. However, the existing porous biomass charcoal material is usually prepared by KOH, K 2 CO 3 The specific surface area is small, and the specific capacitance and energy density of the electrode material prepared by the porous biomass charcoal material are low.
Disclosure of Invention
The invention provides a preparation method of nitrogen-doped active carbon and a multi-hydroxide/biomass porous carbon nano composite electrode material, aiming at solving the technical problem that the specific surface area of a porous biomass carbon material prepared by the existing method is small.
The preparation method of the nitrogen-doped active carbon comprises the following steps:
1. freeze-drying the cleaned corncobs by using a freeze dryer to obtain dried corncobs;
2. mixing dried corncob with NH 4 HCO 3 Uniformly mixing according to the mass ratio of 1 (2-5), and placing the mixture into a pipe typeIn furnace, in N 2 Heating to 700-1000 ℃ in the atmosphere, keeping for 1-5 h for carbonization, cooling and taking out to obtain a carbide;
3. and washing the carbide with 1M hydrochloric acid and deionized water in sequence, and finally drying in a drying oven at the temperature of 50-80 ℃ for 10-16 h to obtain the nitrogen-doped activated carbon. Denoted NAC.
Furthermore, the temperature rise rate in the second step is 4-8 ℃ min -1 。
The method for preparing the multi-hydroxide/biomass porous carbon nano composite electrode material by using the prepared nitrogen-doped activated carbon comprises the following steps:
1. according to the atomic ratio of Ni: (Co + Al) =1: (0.5 to 1) and Co: al =1: (0-1) mixing NiSO 4 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、AlCl 3 ·6H 2 Dissolving O and nitrogen-doped active carbon in deionized water, and stirring and ultrasonically treating for 20-50 minutes to obtain a precursor solution;
2. mixing the precursor solution with ammonia water (NH) 3 ·H 2 O) is transferred into a high-pressure kettle, then the temperature is raised to 130-160 ℃, the temperature is kept for 3-6 hours, then the filtration is carried out, the solid phase is washed by ethanol and deionized water in sequence, and the vacuum drying is carried out, thus obtaining the multi-hydroxide/biomass porous carbon nano composite electrode material. Expressed as Co-Ni LDH/NAC or Al-Co-Ni LDH/NAC.
Furthermore, the concentration of the nitrogen-doped active carbon in the precursor liquid in the step one is 1-2 mg/mL;
further, niSO is present in the precursor solution in step one 4 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O and AlCl 3 ·6H 2 The total concentration of O is 0.03-0.1 mmol/mL;
furthermore, the temperature of the vacuum drying in the step two is 50-80 ℃, the vacuum degree is-0.08 MPa to-0.095 MPa, and the drying time is 10-16 h.
Furthermore, in the second step, the mass percentage concentration of the ammonia water is 25-28%; the volume ratio of the precursor solution to 25-28% ammonia water is 1: (0.01-0.1).
In the first step, ni: (Co + Al) =1: (0.5 to 1) and Co: al =1:0, al atoms are not taken, and the obtained product is a binary hydroxide/biomass porous carbon nano composite electrode material and is expressed by Ni-Co/NAC.
The invention takes corncobs as main bodies and adopts NH 4 HCO 3 The N-doped active carbon is an activating agent, replaces the traditional KOH and the like, is obtained by one-step high-temperature carbonization, can increase active sites, construct graded apertures, improve the specific surface area, optimize an electron/ion transmission channel and provide a growth platform for subsequent metal hydroxides. The specific surface area of the nitrogen-doped active carbon reaches 800m 2 g -1 ~900m 2 g -1 . Is 21 to 24 times of the specific surface area of common activated carbon.
The invention also adopts a one-step hydrothermal method to grow Ni-Co or Ni-Co-Al nanosheets on a nitrogen-doped activated carbon (NAC) substrate to obtain the Co-Ni LDH/NAC or Al-Co-Ni LDH/NAC multi-metal doped porous carbon composite material. The binary or ternary layered hydroxide is anchored on the nitrogen-doped active carbon substrate to obtain the high-performance composite material. After the capacitor is assembled, the specific capacitance of Al-Co-Ni LDH/NAC reaches 1280-1836.7 Fg -1 The specific capacitance of Co-Ni LDH/NAC reaches 800-1300F g -1 The specific capacitance of NAC reaches 240-450F g -1 . The composite material has excellent electrochemical performance and rapid redox reaction kinetics, is an ideal electrode material, can obtain a high-energy density electrode material, and can improve the stability and rate capability of the material.
Drawings
FIG. 1 is a scanning electron micrograph of materials prepared in examples 1 to 4;
FIG. 2 is an XPS spectrum of the materials prepared in examples 1-4;
FIG. 3 is N of the materials prepared in examples 1 to 4 2 Adsorption curve diagram;
FIG. 4 is a plot of the pore size distribution of the materials prepared in examples 1-4;
FIG. 5 is a cyclic voltammogram of the materials prepared in examples 1 to 4;
FIG. 6 is a constant current charge and discharge diagram of the materials prepared in examples 1 to 2;
FIG. 7 is a constant current charge and discharge plot of the materials prepared in examples 3-4;
FIG. 8 is a graph of energy density versus power density for a capacitor Al-Co-Ni LDH/NAC// NAC;
FIG. 9 is a graph of rate capability for materials prepared in examples 1-4.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: this example directly carbonizes corncobs to prepare comparative activated carbons, and the specific steps are as follows:
1. freeze-drying the cleaned corncob for 24 hours by using a freeze dryer under the conditions that the temperature is-55 ℃ and the vacuum degree is 10Pa to obtain the dried corncob;
2. placing 3 g of dried corncob in a heating furnace at 5 deg.C for min -1 The temperature is raised to 800 ℃ at the speed, the carbonization is carried out for 2 hours, and the temperature is reduced and the active carbon is taken out to obtain the active carbon for comparison. Denoted by AC.
Example 2: the preparation method of the nitrogen-doped activated carbon of the embodiment is carried out according to the following steps:
1. freeze-drying the cleaned corncob for 24 hours by using a freeze dryer under the conditions that the temperature is-55 ℃ and the vacuum degree is 12Pa to obtain the dried corncob;
2. mixing 3 g of dried corncob with 9 g of NH 4 HCO 3 Mixing, heating in a furnace under N 2 At 5 deg.C for min under atmosphere -1 Heating to 800 ℃, keeping for 2 hours for carbonization, cooling and taking out to obtain a carbide;
3. and washing the carbide with 1M hydrochloric acid and deionized water in sequence, and finally drying in a furnace at the temperature of 60 ℃ for 12 hours to obtain the nitrogen-doped activated carbon. Denoted NAC.
Example 3: the method for preparing the multi-hydroxide/biomass porous carbon nano composite electrode material by using the nitrogen-doped activated carbon prepared in the embodiment 2 comprises the following steps:
1. 1mmol of NiSO 4 ·6H 2 O and0.5mmol Co(NO 3 ) 2 ·6H 2 dissolving O and 50mg of nitrogen-doped active carbon in 35mL of deionized water, and stirring and ultrasonically treating for 30 minutes to obtain a precursor solution;
2. 35mL of the precursor solution and 1mL of ammonia water (NH) with the mass percentage concentration of 25 percent 3 ·H 2 O) is transferred into an autoclave with the volume of 50mL, then the temperature is raised to 150 ℃ and kept for 5 hours, then filtration is carried out, the solid phase is washed by ethanol and deionized water in sequence, and then vacuum drying is carried out for 12 hours under the conditions of 60 ℃ and the vacuum degree of-0.095 MPa, so as to obtain the binary hydroxide/biomass porous carbon nano composite electrode material. Expressed as Co-Ni LDH/NAC.
Example 4: the method for preparing the multi-hydroxide/biomass porous carbon nano composite electrode material by using the nitrogen-doped activated carbon prepared in the embodiment 2 comprises the following steps:
1. 1mmol of NiSO 4 ·6H 2 O、0.5mmol Co(NO 3 ) 2 ·6H 2 O and 0.3mmol AlCl 3 ·6H 2 Dissolving O and 50mg of nitrogen-doped active carbon in 35mL of deionized water, and stirring and ultrasonically treating for 30 minutes to obtain a precursor solution;
2. 35mL of the precursor solution and 1mL of ammonia water (NH) with the mass percentage concentration of 25 percent 3 ·H 2 O) is transferred into an autoclave with the volume of 50mL, then the temperature is raised to 150 ℃ and kept for 5 hours, then filtration is carried out, the solid phase is washed by ethanol and deionized water in sequence, and then vacuum drying is carried out for 12 hours under the conditions of 60 ℃ and the vacuum degree of-0.095 MPa, so as to obtain the ternary hydroxide/biomass porous carbon nano composite electrode material. Expressed as Al-Co-Ni LDH/NAC.
Scanning electron micrographs of the materials prepared in examples 1 to 4 were tested, as shown in fig. 1, wherein a is the scanning electron micrograph of activated carbon AC prepared in example 1 as a comparison, b is the scanning electron micrograph of nitrogen-doped activated carbon NAC prepared in example 2, c is the scanning electron micrograph of Co-Ni LDH/NAC prepared in example 3, and d is the scanning electron micrograph of Al-Co-Ni LDH/NAC prepared in example 4. As can be seen from FIG. 1, the one prepared directly after carbonization is used as a pairThe activated carbon AC of the ratio shows a layered block structure, while the nitrogen-doped activated carbon NAC prepared in example 2 is due to NH 4 HCO 3 The generated gas expands the activated carbon layer, creating hierarchical pores. The binary hydroxide/biomass porous carbon nanocomposite electrode material Co-Ni LDH/NAC prepared in example 3 is a blocky stacked nanosheet, the ternary hydroxide/biomass porous carbon nanocomposite electrode material Al-Co-Ni LDH/NAC prepared in example 4 is a hierarchical structure of interconnected nanosheets, the top of the nanosheets are cross-connected slices, the bottom of the nanosheets are stacked slices, and certain gaps can be reserved between the nanosheets, so that effective permeation and ion transmission of electrolyte are facilitated.
The XPS spectra of the materials prepared in examples 1 to 4 were measured, and as shown in fig. 2, it can be seen from fig. 2 that the peaks of NAC were assigned to O1s, N1 s, and C1 s, respectively, indicating successful doping of N element. In addition, XPS spectra show six peaks for Ni 2p, co 2p, O1s, N1 s, C1 s, and Al 2p, indicating the successful preparation of Co-Ni LDH/NAC and Al-Co-Ni LDH/NAC.
N testing of materials prepared in examples 1 to 4 2 The adsorption curve, as shown in FIG. 3, from FIG. 3, it can be seen that the specific surface area of NAC is 879.2m 2 g -1 And the specific surface area of Co-Ni LDH/NAC is 537.3m 2 g -1 The specific surface area of Al-Co-Ni LDH/NAC is 485.9m 2 g -1 Their specific surface areas are all higher than that of activated carbon AC, which is 37.9m 2 g -1 The ammonium bicarbonate modified active carbon is proved to be capable of effectively improving the specific surface area, further enlarging the contact area between the active carbon and an electrolyte and improving the electrochemical performance. FIG. 4 is a plot of the pore size distribution of the materials prepared in test examples 1-4, and as can be seen from FIG. 4, the average pore size of Al-Co-Ni LDH/NAC is 4.1nm, the average pore size of Co-Ni LDH/NAC is 7.7nm, the average pore size of NAC is 14.4nm, the average pore size of AC is 7.6nm, the average pore size of Al-Co-Ni LDH/NAC is smaller than that of Co-Ni LDH/NAC, NAC and AC, and a reasonable pore size distribution can promote the mass transfer process and improve the electrochemical performance.
The cyclic voltammograms and the constant current charge and discharge graphs of the materials prepared in examples 1 to 4 are tested, the cyclic voltammograms are shown in fig. 5, the constant current charge and discharge graphs are shown in fig. 6 and fig. 7, and as can be seen from fig. 5, 6 and 7, the integrated areas of the CV curves of Al-Co-Ni LDH/NAC, co-Ni LDH/NAC and NAC are all larger than that of AC, the integrated area of the CV curve of Al-Co-Ni LDH/NAC is the largest, and the maximum constant current charge and discharge time is possessed, so that the specific capacitance of Al-Co-Ni LDH/NAC is higher, and a three-metal system can provide more active sites, improve the electronic structure and the local coordination environment and promote the electrochemical performance. Meanwhile, due to the fact that the ion diffusion channel is optimized through doping of the multi-metal ions, the capacitance performance and the rate performance of the Al-Co-Ni LDH/NAC and Co-Ni LDH/NAC composite materials are superior to those of nitrogen-doped active carbon.
The capacitor was assembled from Al-Co-Ni LDH/NAC prepared in example 4 and AC, expressed as Al-Co-Ni LDH/NAC// AC, and the energy density of the capacitor was tested as a function of the power density, as shown in FIG. 8, which is seen from FIG. 8 at 6055W kg -1 The capacitor maintains 50.46Wh kg at high power density -1 The ideal energy density of Al-Co-Ni LDH/NAC// AC shows the potential of Al-Co-Ni LDH/NAC// AC as a future energy storage device.
The rate performance of the materials prepared in examples 1-4 was tested and, as shown in FIG. 9, it can be seen from FIG. 9 that NAC, co-Ni LDH/NAC, and Al-Co-Ni LDH/NAC all have higher capacitance retention than AC, with Al-Co-Ni LDH/NAC having the most excellent capacitance retention. The specific capacitance of Al-Co-Ni LDH/NAC reaches 1280-1836.7 Fg -1 The specific capacitance of Co-Ni LDH/NAC reaches 800-1300F g -1 The specific capacitance of NAC reaches 240-450 F.g -1 And the specific capacitance of AC is only 50-150F g -1 . Thus, the specific capacitances of the Al-Co-Ni LDH/NAC, NAC of the present invention are greatly improved relative to AC.
Example 5: the preparation method of the nitrogen-doped activated carbon of the embodiment comprises the following steps:
1. freeze-drying the cleaned corncob for 24 hours by using a freeze dryer under the conditions that the temperature is-55 ℃ and the vacuum degree is 12Pa to obtain the dried corncob;
2. mixing 3 g of dried corncob with 14 g of NH 4 HCO 3 Mixing uniformlyIs put into a heating furnace, under N 2 At 5 deg.C for min under atmosphere -1 Heating to 700 ℃ at the speed, keeping for 3h for carbonization, cooling and taking out to obtain a carbide;
3. and washing the carbide with 1M hydrochloric acid and deionized water in sequence, and finally drying in a furnace at the temperature of 60 ℃ for 12 hours to obtain the nitrogen-doped activated carbon. Denoted NAC.
NAC obtained in this example had a specific surface area of 432.6m 2 g -1 。
Example 6: the method for preparing the multi-hydroxide/biomass porous carbon nano composite electrode material by using the nitrogen-doped activated carbon prepared in the embodiment 5 comprises the following steps:
1. 1mmol of NiSO 4 ·6H 2 O and 0.8mmol Co (NO) 3 ) 2 ·6H 2 Dissolving O and 50mg of nitrogen-doped active carbon in 35mL of deionized water, and stirring and ultrasonically treating for 30 minutes to obtain a precursor solution;
2. 35mL of the precursor solution and 1mL of ammonia water (NH) with the mass percentage concentration of 25 percent 3 ·H 2 O) is transferred into an autoclave with the volume of 50mL, then the temperature is raised to 160 ℃ and kept for 4 hours, then filtration is carried out, the solid phase is washed by ethanol and deionized water in sequence, and then vacuum drying is carried out for 12 hours under the conditions of 60 ℃ and the vacuum degree of-0.095 MPa, so as to obtain the binary hydroxide/biomass porous carbon nano composite electrode material. Expressed as Co-Ni LDH/NAC.
Example 7: the method for preparing the multi-hydroxide/biomass porous carbon nano composite electrode material by using the nitrogen-doped activated carbon prepared in the embodiment 5 comprises the following steps:
1. 1mmol of NiSO 4 ·6H 2 O、0.6mmol Co(NO 3 ) 2 ·6H 2 O and 0.2mmol AlCl 3 ·6H 2 Dissolving O and 50mg of nitrogen-doped active carbon in 35mL of deionized water, and stirring and ultrasonically treating for 30 minutes to obtain a precursor solution;
2. 35mL of the precursor solution and 1mL of ammonia water (NH) with the mass percentage concentration of 25 percent 3 ·H 2 O) was transferred to an autoclave having a volume of 50mL, then heated to 160 ℃ for 4 hours, and then filtered, and the solid was sequentially subjected to ethanol and deionizationWashing with water, and vacuum drying at 60 deg.C under-0.095 MPa for 12h to obtain ternary hydroxide/biomass porous carbon nano composite electrode material. Expressed as Al-Co-Ni LDH/NAC.
The specific capacitance properties of the materials prepared in examples 5 to 7 were tested and the results show that: the specific capacitance of NAC reaches 200-440F g -1 The specific capacitance of Co-Ni LDH/NAC reaches 760-1280 F.g -1 The specific capacitance of Al-Co-Ni LDH/NAC reaches 1300-1805.6 Fg -1 。
Co-Ni LDH/NAC prepared in example 6 and Al-Co-Ni LDH/NAC prepared in example 7 are assembled with NAC to form a capacitor, and the specific capacitance of the tested capacitor can reach 200-230 Fg g/g as shown by Co-Ni LDH/NAC// NAC and Al-Co-Ni LDH/NAC// NAC -1 。
Claims (3)
1. The method for preparing the multicomponent hydroxide/biomass porous carbon nano composite electrode material by using the nitrogen-doped activated carbon is characterized by comprising the following steps:
1. according to the atomic ratio of Ni: (Co + Al) =1: (0.5 to 1) and Co: al =1: (0.6-1) mixing NiSO 4 . 6H 2 O、Co(NO 3 ) 2 . 6H 2 O、AlCl 3 . 6H 2 Dissolving O and nitrogen-doped active carbon in deionized water, and stirring and ultrasonically treating for 20-50 minutes to obtain a precursor solution; wherein the concentration of the nitrogen-doped active carbon in the precursor liquid is 1-2 mg/mL; niSO in precursor solution 4 . 6H 2 O、Co(NO 3 ) 2 . 6H 2 O and AlCl 3 . 6H 2 The total concentration of O is 0.03-0.1 mmol/mL;
the preparation method of the nitrogen-doped activated carbon comprises the following steps:
freezing and drying the cleaned corncobs by using a freezing dryer to obtain dried corncobs;
(II) mixing the dried corncob with NH 4 HCO 3 Uniformly mixing the components according to the mass ratio of 1 (2-5), putting the mixture into a tube furnace, and adding the mixture into a furnace at the temperature of N 2 Heating to 700-1000 ℃ in the atmosphere, keeping for 1-5 h for carbonization, cooling and taking out to obtain the productTo a char;
washing the carbide with 1M hydrochloric acid and deionized water in sequence, and finally drying in a drying oven at the temperature of 50-80 ℃ for 10-16 h to obtain the nitrogen-doped activated carbon;
2. transferring the precursor solution and ammonia water into a high-pressure kettle, heating to 130-160 ℃, keeping for 3-6 hours, filtering, washing the solid phase with ethanol and deionized water in sequence, and drying in vacuum to obtain the multi-hydroxide/biomass porous carbon nano composite electrode material.
2. The preparation method of the multi-hydroxide/biomass porous carbon nanocomposite electrode material according to claim 1, wherein the temperature of vacuum drying in the second step is 50-80 ℃, the vacuum degree is 0.08-0.095 MPa, and the drying time is 10-16 h.
3. The preparation method of the multi-hydroxide/biomass porous carbon nano composite electrode material according to claim 1, characterized in that in the second step, the mass percentage concentration of ammonia water is 25% -28%; the volume ratio of the precursor solution to 25-28% ammonia water is 1: (0.01-0.1).
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